An efficient catalytic system containing [RuCl2(η6-p-cymene)]2 and one P,N ligand, N-diphenylphosphino-2-aminopyridine (L1) was loaded in catalyzing the alkylation of ketones with primary alcohols for a diverse array of substrates. Other five P,N ligands based on pyridin-2-amine and pyrimidin-2-amine were also examined in this reaction to explore the influence of steric hindrance and electronic effects. Monitoring by 1H NMR and ESI-MS reveals a stable cationic L1-coordinated ruthenium hydride intermediate, identified as [Ru(η6-p-cymene)(κ2-L1)H]+. Organic intermediates consistent with a three-step dehydrogenation, alkylation and hydrogenation pathway were also observed. The final step in this reaction, the ruthenium-catalysed transfer hydrogenation reduction of α,β-unsaturated ketone with benzyl alcohol was performed separately.